US3438937A - Process for curing polyepoxides and resulting products - Google Patents

Process for curing polyepoxides and resulting products Download PDF

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US3438937A
US3438937A US404909A US3438937DA US3438937A US 3438937 A US3438937 A US 3438937A US 404909 A US404909 A US 404909A US 3438937D A US3438937D A US 3438937DA US 3438937 A US3438937 A US 3438937A
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polyepoxides
curing
imidazole
parts
polyepoxide
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Samuel H Christie
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Shell USA Inc
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Shell Oil Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen

Definitions

  • the invention further provides hard resinous products obtained by the above-described process.
  • Polyepoxides such as, for example, those obtained by reacting epichlorohydrin with polyhydric phenols in the presence of caustic, are promising materials for use in many industrial applications as they can be reacted with curing agents to form insoluble infusible products having good chemical resistance.
  • Many conventional polyepoxide curing agent systems have certain drawbacks that greatly limit the industrial use of the polyepoxides.
  • the known mixtures comprising the polyepoxides and aliphatic amines set up rather rapidly, and this is true even though the mixtures are stored in air tight containers away from moisture and air. This difiiculty necessitates mixing of the components just before use and rapid use of the material before cure sets in. Such a procedure places a considerable burden on the individual operators, and in many cases, gives inferior products because of the inefficient mixing and too rapid operations.
  • these compounds include, among others, the imidazoles, such as compounds of the formula alkenyl ring and the like.
  • X is a hydrogen or a hydrocarbon radical, and preferably an alkyl, cycloalkyl, cycloalkenyl, aryl, alkaryl or arylalkyl radicals, and particularly those containing no more than 15 carbon atoms.
  • Example of such compounds include, among others, 2-ethyl-4-methyl imidazole, 4 *butyl 5 ethyl imidazole, 2 cyclohexyl- 4-methyl imidazole, 2-butoxy-4-allyl imidazole, 2-carboethoxybutyl-4-methyl imidazole, 2-octyl-4-hexyl imidazole, and 2-ethyl-4-phenyl imidazole, and mixtures thereof.
  • R is selected from hydrogen, halogen, or an organic radical, such as a hydrocarbon radical or substituted hydrocarbon radical, for example, an ester, ether, amide, imide, amino, halogen or mercapto-substituted hydrocarbon radical, said organic radicals preferably containing up to 15 carbon atoms, and still more preferably up to 8 carbon atoms.
  • R is selected from hydrogen, halogen, or an organic radical, such as a hydrocarbon radical or substituted hydrocarbon radical, for example, an ester, ether, amide, imide, amino, halogen or mercapto-substituted hydrocarbon radical, said organic radicals preferably containing up to 15 carbon atoms, and still more preferably up to 8 carbon atoms.
  • Examples of such compounds include, among others, 'benzimidazole, methylbenzimid'azole, dimethylbenzimidazole, chlorobenzimidazole, mercaptobenzimidazole, methoxybenzimidazole and the like, and mixtures thereof.
  • the above-described imidazoles can be prepared by conventional techniques of reacting a dialdehyde with ammonia and formaldehyde.
  • the polyepoxides to be used in preparing the compositions of the present invention comprise those materials possessing more than one vicinal epoxy group, i,e., more than one group. These compounds may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and may be substituted with substituents, such as chlorine, hydroxyl groups, either radicals and the like. They may be monomeric or polymeric.
  • polyepoxides for clarity, many of the polyepoxides and particularly those of the polymeric type are described in terms of epoxy equivalent values. The meaning of this expression is described in U.S. 2,633,458.
  • the polyepoxides used in the present process are those having an epoxy equivalency greater than 1.0.
  • epoxidized esters of the polyethylenically unsaturated monocarboxylic acids such as epoxidized linseed, soybean, perilla, oiticia, tung, walnut and dehydrated castor oil, methyl linoleate, butyl linoleate, ethyl 9,12-octadecandienoate, butyl 9,12,15- octadecatrienoate, butyl eleostearate, monoglycerides of tung oil fatty acids, monoglycerides of soybean oil, sunflower, rapeseed, hempseed, sardine, cottonseed oil, and the like.
  • epoxy-containing materials used in the process of the inventon include the epoxidized esters of unsaturated monohydric alcohols and polycarboxylic acids, such as, for example, di(2,3epoxybutyl) adipate, di(2,3epoxybutyl) oxalate, di(2,3-epoxyhexyl) succinate, di(3,4-epoxybutyl) maleate, di(2,3-epoxyoctyl) pimelate, di(2,3epoxybutyl) phthalate, di(2,3epoxyootyl) tetrahydrophthalate, di(4,5-epoxydodecyl) male ate, di(2,3epoxybutyl) terepht-halate, di(2,3-epoxypentyl) thiodipropionate, di(5,6-epoxytetradecyl) diphenyldicarboxylate, di
  • epoxy-containing materials includes those epoxidized esters of unsaturated alcohols and unsaturated carboxylic acids, such as 2,3-epoxybutyl 3,4-
  • Still another group of the epoxy-containing materials included epoxidized derivatives of polyethylenically unsaturated polycarboxylic acids such as, for example, dimethyl 8,9,12,l3-diepoxyeicosanedioate, dibutyl 7,8,11, 12-diepoxyoctadecanedioate, dioctyl l0,ll-diethyl-8,9,12, 13-diepoxy-eiconsanedioate, dihexyl 6,7,10,11-diepoxyhexadecanedioate, didecyl 9-epoxy-ethyl-l0,ll-epoxyoctadecanedioate, dibutyl 3-butyl-3,4,5,6-diepoxycyclohexane-1,2-dicarboxylate, dicyclohexyl 3,4,5,6-diepoxycyclohexane-1,2-dicarboxylate, dibenzyl 1,
  • Still another group comprises the epoxidized polyesters obtained by reacting an unsaturated polyhydric alcohol and/ or unsaturated polycarboxylic acid or anhydride groups, such as, for example, the polyester obtained by reacting 8,9,12,13-eicosanedienedioic acid with ethylene glycol, the polyester obtained by reacting diethylene glycol with 2-cyclohexene-1,4-dicarboxylic acid and the like, and mixtures thereof. 7
  • Still another group comprises the epoxidized polyethylenically unsaturated hydrocarbons, such as epoxidized 2,2-bis(2-cyclohexenyl) propane, epoxidized vinyl cyclohexene and epoxidized dimer of cyclopentadiene.
  • epoxidized polyethylenically unsaturated hydrocarbons such as epoxidized 2,2-bis(2-cyclohexenyl) propane, epoxidized vinyl cyclohexene and epoxidized dimer of cyclopentadiene.
  • Another group comprises the epoxidized polymers and copolymers of diolefins, such as butadiene.
  • diolefins such as butadiene.
  • examples of this include, among others, butadiene, acrylonitrile copolymers (Hycar rubbers) butadiene-styrene copolymers and the like.
  • Another group comprises the glycidyl containing nitrogen compounds, such as diglycidyl aniline and diand triglycidylamine.
  • the polyepoxides that are particularly preferred for use in the compositions of the invention are the glycidyl ethers and particularly the glycidyl ethers of polyhydric phenols and polyhydric alcohols.
  • the glycidyl ethers of polyhydric phenols are obtained by reacting epichlorohydrin with the desired polyhydric phenols in the presence of alkali.
  • Polyether A and Polyether B described in the above-noted U.S. 2,633,458 are good examples of polyepoxides of this type.
  • Other examples include the polyglycidyl ether of 1,1,2,2-tetrakis(4-hydroxyphenyl) ethane (epoxy value of 0.45 eq/ 100 g.
  • polyglycidyl ether of 1,1,5,5tetrakis(hydroxyphenyl) pentane epoxy value of 0.514 eq/ g.
  • Other examples include the glycidated novolacs as obtained by reacting epichlorohydrin with hovon resins obtained by condensation of aldehyde with polyhydric phenols.
  • the heterocyclic curing agent is preferably employed in amounts varying from about 0.1% to about 50% by weight of the polyepoxide, and still more preferably from 5 to 30% by weight of the polyepoxide.
  • the heterocyclic curing agent can be used in combination with other components such as phenols, mercaptans, triphenyl phosphorus, triphenyl arsenic, triphenyl antimony, amines, amine salts or quaternary ammonium salts, etc.
  • Preferred additives include the mercaptans, phenols, triphenyl phosphorus and the amines, such as, for example, benzyldimethylamine, dicyandiamide, p,p'-bis(dimethylaminophenyl) methan, pyridine, dimethyl aniline, benzyldimethylamine, dimethylethanolamine, methyldiethanolamine, morpholine, dimethylaminopropylamine, dibutylaminopropylamine, stearyldimethylamine, tri-n-butylamine, triamylamine, tri-n-hexylamine, ethyl di-n-propylamine, phenylene diamine, diethylene triamine and the like, and mixtures thereof.
  • the salts may be exemplified by the inorganic and organic acid salts of the amines,
  • the quaternary ammonium salts may be exemplified by the following: benzyltrimethylammonium chloride, phenyltributylammonium chloride, cyclohexyltributylammonium sulfate, benzyltrimethylammonium sulfate, benzyltrimethylammonium borate, diphenyldioctylammonium chloride, and the like, and mixtures thereof.
  • additives include polybasic anhydrides, such as, for example, phthalic anhydride, tetrahydrophthalic anhydride, methyl-3-,6- endomethylene-4-tetrahydrophthalic anhydride, chlorendic anhydride, pyromellitic dianhydride, and the like, and the corresponding acids.
  • polybasic anhydrides such as, for example, phthalic anhydride, tetrahydrophthalic anhydride, methyl-3-,6- endomethylene-4-tetrahydrophthalic anhydride, chlorendic anhydride, pyromellitic dianhydride, and the like, and the corresponding acids.
  • additives are generally employed in amounts varying from 0.1 parts to 25 parts per 100 parts of polyepoxide, and preferably from 1 part to 5 parts per 100 parts of polyepoxide.
  • the curing of the polyepoxides may be accomplished by merely mixing the polyepoxides with the heterocyclic curing agent and heating the combined mixture. If the polyepoxide is a solid or if the heterocyclic curing agent is somewhat viscous or solid, the mixing may be accomplished by heating the components or by use of common solvents. Suitable common solvents include benzene, toluene, cyclohexane, ketones, ethers, esters, nitriles, and the like. Monoepoxy diluents, such as butyl glycidyl ether, phenyl glycidyl ether, and the like may also be employed. One may also employ nonreactive diluents, such as coal tars, refined coal tars, coal tar pitches, asphalts, pine tar, pine oil, extracts of lube oil distillates, and the like.
  • nonreactive diluents such as coal tars, refined coal tar
  • temperatures employed during the cure may vary over a wide range. In general, temperatures ranging from about 40 to 300 C. will give satisfactory results. Preferred temperatures range from about 50 to 250 C.
  • the resinified products obtained by the above-described process have surprisingly high heat deflection temperature and strength values at elevated temperatures. In addition, they display good resistance to boiling water and powerful solvents and chemicals. These unusual properties make the process of particular value in the preparation of adhesives, laminates and molded articles.
  • compositions of the invention are particularly useful for filament winding applications.
  • the filaments such as, for example, glass fibers
  • the liquid compositions of the invention are passed into and through the liquid compositions of the invention and then wound onto the desired mandrel or form and the formed unit allowed to cure, preferably by application of heat.
  • the great advantage of the new compositions in this application is the fact that the compositions can be cured at low temperatures and their use would not affect heat sensitive material being used in the application.
  • the rubber lining of missile cases are heat sensitive and would be affected by the use of high temperatures in curing filaments wound thereon.
  • the new com positions thus could be used for the filament winding of these cases where the winding is directly on the liner.
  • compositions of the invention are also particularly useful for encapsulation of electrical or other types of equipment. In many cases it is important to hold such apparatus or equipment in rigid position so that the tubes or other delicate pieces will not be jarred out of position.
  • the epoxy resins are particularly useful for this application because of their good non-conducting properties. The need for heat in curing the epoxy resin, however, had limited their application in this field.
  • the present compositions, however, that can be cured at lower temperatures will find wide use in this field. In such operations, the desired polyepoxide and heterocyclic curing agent are mixed together and the resulting mixture poured in a mold which surrounds the electrical apparatus. After application of slight amount of heat, the composition sets up to the hard cured casting and the encapsulated apparatus can be removed from the mold.
  • the new compositions of the invention are also useful as adhesives. In this application they can be used as a 6 paste or solution depending on the method of preparation as described above.
  • Other materials may also be included in the composition, such as pigments, plasticizers, stabilizers and reinforcing fillers, such as aluminum powder, asbestos, powdered mica, zinc dust, bentonite, ground glass fibers, monetta clay and the like. These fillers are preferably used in amounts varying from about 10 parts to 200 parts per parts of the polyepoxide and curing agent.
  • resins such as phenol-aldehyde resins, urea-aldehyde resins, furfural resins, polyacetal resins, polycarbonate resins, polyamide resins, and the like.
  • compositions may be used in the bonding of a great variety of difierent materials, such as metal-to-metal to other materials, such as plastic, wood-to-wood, glass-toglass, glass-to-metal, and the like. They are of particular value, however, in the bonding of metals such as aluminum-to-aluminum and steel-to-steel.
  • difierent materials such as metal-to-metal to other materials, such as plastic, wood-to-wood, glass-toglass, glass-to-metal, and the like. They are of particular value, however, in the bonding of metals such as aluminum-to-aluminum and steel-to-steel.
  • the compositions When applied as an adhesive, the compositions may simply be spread on the desired surface to form films of various thicknesses, e.g., 0.5 mils to 30 mils, and then the other surface superimposed and heat applied. Curing pressures can be light contact pressures up to about 500 psi.
  • compositions are also useful for preparing laminates.
  • the sheets of fibrous material are first treated with the mixture of polyepoxide and curing agent. This is conveniently accomplished by spreading the paste or solution containing the abovenoted mixture onto the sheets of glass cloth, paper, textiles, etc.
  • the sheets are then superimposed and the assembly cured under heat and pressure.
  • the assembly is preferably cured in a heated press under a pressure of about 25 to 500 or more pounds per square inch and temperatures of about 100 to 300 C.
  • the resulting laminate is extremely strong and resistance against heat and the action of organic and corrosive solvents.
  • the fibrous material used in the preparation of the laminates may be of any suitable material, such as glass cloth and matting, paper, asbestos paper, mica flakes, cotton bats, duck muslin, canvas, synthetic fibers, such as nylons, Dacron, and the like. It is usually preferred to utilize woven glass cloth that has been given prior treatment with well known finishing or sizing agents, therefore, such as chrome methacrylate or vinyl trichlorosilane.
  • EXAMPLE I This example illustrates the use of 2-ethyl-4-methyl imidazole to cure Polyether A [i.e., a glycidyl ether of 2,2-bis (4-hydroxyphenyl) propane]
  • Polyether A i.e., a glycidyl ether of 2,2-bis (4-hydroxyphenyl) propane
  • One hundred parts of Polyether A was combined with 10 parts of 2-ethyl-4-methyl imidazole, This composition when kept at room temperature had a pot life of 8 hours.
  • a portion of the composition cured for 8 hours at 60 C. was converted to a hard insoluble infusible casting having excellent heat distortion temperature, hardness, strength and chemical resistance.
  • the heat distortion temperature and strength values are shown in the following table (A) in comparison to HDT values and strengths and related compositions prepared by the use of conventional aromatic curing agent metaphenylene diamine (14.3 parts) which was cured 2 hours at 80 C. and 2 hours at C., (B) and another conventional curing agent tri(2-ethylhexoic acid) salt of tri(dimethylaminomethylphenol) cured at 60 C. for 8 hours (12 parts) (C):
  • Polyether A One hundred parts of Polyether A were combined with 10 parts of 2-ethyl-4-methyl imidazole and the mixture used in a filament Winding application to prepare Naval Ordnance Laboratory (NOL) rings.
  • NOL Naval Ordnance Laboratory
  • glass fibers (12-end E-HTS glass) were passed into and through this composition and then wound on a mandrel to form the ring.
  • the resulting product was cured for 8 hours at 60 C. and the resin content was 15%.
  • EXAMPLE V About 100 parts of diglycidyl ether of resorcinol are combined with 15 part of 2-hexyl-4-phenyl imidazole and the mixture heated at 70 C. for several hours. The resulting product is a hard insoluble infusible product having good high temperature properties.
  • EXAMPLE VI About 100 parts of a glycidated novolac resin obtained by reacting a phenol-formaldehyde condensate with epichlorohydrin is mixed with 15 parts of 2-ethyl-4-methyl imidazole. This mixture is heated to 70 C. for several hours. The resulting product is a hard insoluble infusible product having good high temperature properties.
  • Example I is repeated with the exception that Polyether A is replaced by a 50:50 mixture of Polyether A and epoxidized methyl cyclohexenyl methylcyclohexenecarboxylate. Related results are obtained.
  • EXAMPLE X The preceding example was repeated with the exception that the ratio of components was 50 parts Polyether A, 50 parts of the tetraglycidyl ether and 15 parts of benzimidazole. The rings were cured for 4 hours at 150 C. The resin content was 24.7%. The resulting product had a horizontal shear strength psi. at 23 C. of 11,800 and at 150 C. of 5,500. Approximate prepreg shelf life in weeks at 23 C. was greater than 10.
  • EXAMPLE XI Example I is repeated with the exception that the curing agent employed is as follows: 2-methyl imidazole, Z-butyl 4-allyl imidazole, 2,5-dichloro 4-ethyl imidazole, 2-methyl 4-mercaptoethyl imidazole, Z-ethyl 4-(2-ethylamino) imidazole and Z-carboethoxybutyl 4-met'hyl imidazole, methylbenzimidazole, dichlorobenzimidazole. Related results are obtained.
  • a process for curing a polyepoxide having more than one vie-epoxy group which comprises mixing and reacting at a temperature above 40 C. the polyepoxide with a curing amount of an imidazole compound of the formula wherein R is a member of the group consisting of hydrogen, halogen, hydrocarbon radicals, halogen-substituted hydrocarbon radicals, ester-substituted hydrocarbon radicals and mercaptan-substituted hydrocarbon radicals.
  • a curable composition comprising a mixture of a polyepoxide possessing more than one vie-epoxy group and a curing amount of an imidazole compound of the formula wherein R is a member of the group consisting of hydrogen, halogen, hydrocarbon radicals, halogen-substituted hydrocarbon radicals, ester-substituted hydrocarbon radicals and mercaptan-substituted hydrocarbon radicals.
  • a curable composition comprising a mixture of (1) a glycidyl polyether of a polyhydric phenol, and (2) from 0.1% to 10% by weight of an imidazole compound of the formula wherein R is a member of the group consisting of hydrogen, halogen, hydrocarbon radicals, halogen-substituted hydrocarbon radicals, ester-substituted hydrocarbon radicals and mercaptan-substituted hydrocarbon radicals.
  • polyepoxide is a glycidyl polyether of a polyhydric phenol having a 1,2-epoxy equivalency between 1.1 and 2.0 and a molecular weight between 200 and 900.
  • a curable composition comprising a polyepoxide having more than one Vic-epoxy group and a curing amount of benzimidazolc.

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US404909A 1963-05-02 1964-10-19 Process for curing polyepoxides and resulting products Expired - Lifetime US3438937A (en)

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Cited By (22)

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US3523037A (en) * 1967-06-12 1970-08-04 Ibm Epoxy resin composition containing brominated polyglycidyl ether of bisphenol a and a polyglycidyl ether of tetrakis(hydroxyphenyl) ethane
US3609116A (en) * 1968-12-06 1971-09-28 Gen Dynamics Corp Moldable shim material for dimensional and aerodynamic surface control of aerospace structure
US3632427A (en) * 1970-05-15 1972-01-04 Air Prod & Chem Epoxy resin and imidazole alkyl acid phosphate fiber treatment
US3637417A (en) * 1967-08-02 1972-01-25 Air Prod & Chem Epoxy silane-imidazole treatment of reinforcement material
US3666755A (en) * 1970-03-26 1972-05-30 Merck & Co Inc 2-imidazolylbicyclo{8 2.2.2{9 octanes
US3755253A (en) * 1971-09-24 1973-08-28 Shell Oil Co Catalization of diaminodiphenylsulfone cure of polyepoxides with an imidazole compound or a salt thereof
US3989673A (en) * 1974-12-30 1976-11-02 Hughes Aircraft Company Low temperature curing resin system
US4060655A (en) * 1974-02-02 1977-11-29 Hoechst Aktiengesellschaft Resin coated metal substrates
US4066625A (en) * 1967-05-02 1978-01-03 Amicon Corporation Unitary curable resin compositions
US4069203A (en) * 1975-10-17 1978-01-17 Shell Oil Company Rapid curing polyepoxide compositions
US4159976A (en) * 1977-03-10 1979-07-03 Loctite Corporation Curable systems containing epoxy resin and methanol or ethanol solvent to suppress the catalytic reaction between epoxy resin and an imidazole catalytic curing agent
US4322459A (en) * 1980-11-21 1982-03-30 Ppg Industries, Inc. Epoxy derived resins containing amino or mercapto substituted azole functionality and compositions containing same
US4331582A (en) * 1980-01-14 1982-05-25 Hitco Epoxy latent catalyst
US4335228A (en) * 1978-02-27 1982-06-15 Air Products And Chemicals, Inc. Isocyanate blocked imidazoles and imidazolines for epoxy powder coating
US4393181A (en) * 1982-06-30 1983-07-12 Shell Oil Company Polyfunctional phenolic-melamine epoxy resin curing agents
US4558077A (en) * 1984-03-08 1985-12-10 General Motors Corporation Epoxy bonded rare earth-iron magnets
US4906711A (en) * 1988-07-29 1990-03-06 General Electric Company Low viscosity epoxy resin compositions
US4912190A (en) * 1987-05-06 1990-03-27 Aeg Isolier- Und Kunststoff Gmbh Epoxy resin formulation having an extremely short hardening time for the production of epoxy glass laminates in continuously operating double-belt presses
US5508328A (en) * 1994-11-17 1996-04-16 Alliedsignal Inc. Curing epoxy resins using dicy, imidazole and acid
US5654081A (en) * 1995-07-05 1997-08-05 Ford Motor Company Integrated circuit assembly with polymeric underfill body
US6492437B1 (en) 2001-06-21 2002-12-10 National Starch And Chemical Investment Holding Corporation Solvent-based process for manufacturing latent curing catalysts
US20050016677A1 (en) * 2003-07-22 2005-01-27 L&L Products, Inc. Two-component adhesive material and method of use therefor

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DE3382736T2 (de) * 1982-09-21 1994-05-26 Ajinomoto Kk Latente Härter für Epoxyharze.

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4066625A (en) * 1967-05-02 1978-01-03 Amicon Corporation Unitary curable resin compositions
US3523037A (en) * 1967-06-12 1970-08-04 Ibm Epoxy resin composition containing brominated polyglycidyl ether of bisphenol a and a polyglycidyl ether of tetrakis(hydroxyphenyl) ethane
US3637417A (en) * 1967-08-02 1972-01-25 Air Prod & Chem Epoxy silane-imidazole treatment of reinforcement material
US3609116A (en) * 1968-12-06 1971-09-28 Gen Dynamics Corp Moldable shim material for dimensional and aerodynamic surface control of aerospace structure
US3666755A (en) * 1970-03-26 1972-05-30 Merck & Co Inc 2-imidazolylbicyclo{8 2.2.2{9 octanes
US3632427A (en) * 1970-05-15 1972-01-04 Air Prod & Chem Epoxy resin and imidazole alkyl acid phosphate fiber treatment
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CH432855A (de) 1967-03-31
NL6404838A (https=) 1964-11-03

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